Solid flavoring compositions containing sucrose esters and process of making the same



SOLID FLAVORING COMPOSITIONS CONTAIN- ING SUCROSE ESTERS AND PROCESS OFMAK- ING THE SANIE Thomas H. Schultz, Lafayette, and William F. Talburt,Berkeley, Calif., assignors to the United States of America asrepresented by the Secretary of Agriculture Application December 22,1958 Serial No. 782,334

4 Claims. (Cl. 99-140 (Granted under Title 35, US. Code (1952), sec.266) No Drawing.

A non-exclusive, irrevocable, royalty-free license in the inventionherein described, throughout the world for all purposes of the UnitedStates Government, with the power to grant sublicenses for suchpurposes, is hereby granted to the Government of the United States ofAmerica.

This invention relates to and has among its objects the provision ofnovel flavoring compositions and methods for producing them. A generalobject of the invention concerns the preparation of solid flavoringcompositions which serve as convenient sources of flavor and in whichthe volatile flavoring principles in the composition are effectivelylocked-in, that is, the flavoring principles are completely surroundedby an edible, solid, imperme able, protective substance whereby thecomposition may be stored for long periods of time without loss offlavoring value through vaporization or deterioration of the flavoringprinciples. A specific object of the invention concerns the preparationof flavoring compositions having the above mentioned properties andwherein the compositions contain particular ingredients which cooperateto prevent loss of the volatile flavoring material from thecompositions. Further objects and advantages of the invention will beevident from the description below, wherein parts and percentages are byweight unless otherwise specified.

It has been proposed heretofore to prepare solid flavoring compositionsby emulsifying a volatile flavoring agent into; a molten sugar base. Thehot emulsion is either (a) cooled to solidify and harden it, then groundinto suitable particles or (b) reduced to particles while still in aliquid to plastic condition and then cooled. The resulting solidifiedemulsion in particulate form is useful for imparting flavor to variousfoods and beverages, e.g., it may be added to dehydrated fruit juiceproducts to restore flavor lost during dehydration.

- It has now been observed that when the products so made are subjectedto analysis, it is found that the amount of volatile flavoring agenttherein is substantially less than the amount thereof originallyincorporated into the sugar base. This is particularly true when theproduct is brought to its desired particle size by crushing or grindingafter the hot emulsion has been hardened by cooling. In typical cases ofthis type it has been determined that the solid composition containsonly 40 to 70% of the flavoring agent originally added to the sugarbase. In general, the higher the proportion of flavoring agent added tothe sugar base, the lower is the percentage retention of the flavoringagent. This factor causes serious difficulties where it is desired toproduce a product of relatively high and uniform, predetermined flavorcontent. Moreover, this situation involves a serious loss of expensiveand valuable flavoringagent.

2,929,722 Patented Mar. 22, 1969 ice When the product is prepared byprocedures which involve subdivision into particles while the emulsionis still in a fluid to plastic state, it has likewise been found thatserious losses of volatile flavoring agent occur. As in the situationnoted above, the percentage loss increases as the proportion offlavoring agent added to the sugar base is increased. H

The loss of flavoring agent is due to a vaporization of this materialduring the steps of preparing the'solid composition. It is believed thatthe underlying'rea'sjon' for the vaporization is the inability of theprior processes to yield an emulsion of liquid sugar base and flavoringagent wherein the size of the globules of the latter is suflicientlysmall. The flavoring agent and the sugar base are, of course, entirelydiverse in their properties; the former being an oily material, thelatter being a water-soluble substance. Because of this fundamentalincompatibiilty, the flavoring agent does not readily blend with thesugar base but exists as relatively large globules. When the flavoringagent-sugar base emulsion is subjected to the various steps required toproduce the final product, for example, grinding or other size reductionstep, a considerable proportion of these globules are exposed to theatmosphere and the flavoring agent vapor-J izes and is lost. 7

In accordance with the invention, the disadvantages described above areobviated by incorporating with the flavoring agent and the sugar base anester of sucrose with a higher fatty acid. By addition of this ester,loss of flavoring agent is virtually eliminated. As a consequence, onemay readily prepare solid compositions containing uniform andpredetermined proportions of flavoring agent. Such products are ofcourse highly desirable from a commercial standpoint asthey lendthemselves readily to direct use in food formulations without thenecessity for pre-testing to ensure proper flavor level. A particularadvantage of the invention is that it enables the preparation ofcompositions containing relatively high proportions of flavoring agentyet without substantial loss of the flavor component. The eflicacy ofthe sucrose esters is believed to be due to the ability of these compounds to form a physical barrier around each particle of flavoringagent and thus prevent the particles from coalescing into largeglobules. The esters thus promote intimate blendingof' the flavoringagent and sugar base. The net result is that the flavoring agent iseffectively protected from vaporization throughout the procedural stepsof preparing the solid compositions and during th subsequent storage ofthe final product.

It is to be noted that the problem of preventing loss of flavoringagentsin sugar base. compositions differs in a number of respects fromemulsification of oils in aque'-' ous systems. Thus in the latter casemany dilferent types of surface active agents may be employed to promoteorstabilize emulsions of oil and water. On the other hand, with theflavoring agent-sugar base emulsions, many conventional emulsifyingagents, including the monoglycerides of higher fatty acids and thepolyoxyethyle'ne sorbitan higher fatty acid esters, are not effective toprevent loss of flavoring agent. It is thus evident that theeffectiveness of the sucrose esters to prevent loss of flavor-' ingagent from sugar base compositions involves a sur? prising result whichcould not'have been predicted meant that not all the hydroxy groups ofthe sucrose are esterified, i.e., one or more hydroxy groups remain assuch. It is generally preferred to employ the compounds wherein one ortwo hydroxy groups are esterified, that is, the mono or diesters. Theacid moiety of the esters may be derived from any higher fatty acid, bywhich term is sucrose ole tet a te. susrss' retal ate-stands. an

the l e The am un of .149 9 e ter to bs mp v sie any particular casewill vary depending on such factors as the .tiharacteristics oftheselected sucrose ester, the nature of the flavoring agent'and thesugar base :the relative proportions of flavoring agent and sugar base,etc. For example, a composition containing a relatively large proportion of flavoring agent will require more of the sucrose ester thanone containing a lesser amount of flavoring agent. In general, theproportion of sucrose ester may range from about (Lite based on the dryweight of the sugar base.

Typically, preparation of solid flavoring compositions in accordancewith the invention involves these steps: Preparation of a molten sugarbase; incorporation of a selected volatile flavoring agent and sucroseester into the base with the aid agitation to obtain an emulsion of theflavoring agent in the molten base; and forming the emulsion into solidmasses of desired shape and/ or size. In preparing the molten sugarbase, two or more sugars maybe mixed and heated to liquefy them.However, to avoid any possibility of charring it is preferredto dissolveor disperse the sugars in water and then boil the solution until itreaches a solids content high enough so that on cooling to roomtemperature it will form a hard glassy mass. In many cases when aboiling point of about 150 C. is attained the solids content is at theproper level. However, this temperature is subject to considerablevariation depending on the proportions of ingredients and in anyparticular case the proper boiling temperature can be ascertained bycooling a small sample of the hot and noting whether or not it forms ahard glassy mass. Aiter having attained the proper solids content, thehot sugar base is preferably cooled somewhat so that when the flavoringagent is incorporated therein the amount of evaporation of the flavoringmaterial will not be excessive. In any event the molten material may becooledas much as desired with the proviso that it remain fluid enough tomix with the flavoring material and fluid enough to flow through theorifice or similar equipment, if such be used to form the solidifiedmasses. Depending on the ingredients, the temperature of the molten basemay be about from 80 to 150 .C. when the flavoring agent is incorporatedtherein. Dextrin, for example, greatly increases the viscosity of thehot base. Thus where no dextrin or at most a small percentage thereof isused the base will remain fluid enough to incorporate the flavoring atlower temperatures than in instances where larger percentages of dextrinare employed. The sucrose estermay be incorporated into the molten sugarbase prior to or simultaneously with the flavoring agent. In

any event for best results the sucrose esterand flavoring agentareincorporated into themolten base without at the same timebeating airinto the mixture.

I The hot, emulsion of flavoring agent, sucrose ester, and sugar baseproduced asdescribed above may thenibe treated in any ofvarious waystoproduce the .solidcoinposition. For example, the hot emulsion may besimply a uage M allowed to cool and solidify then crushed or ground intoparticles of suitable size" In the alternative, thniiilsion may bereduced to particles while still liquid or at least plastic. This can bedone in various ways as by forming the hot emulsion into droplets whichare allowed to congeal in air or by extruding the hot emulsion in acontinuous stream which is subdivided by pinching or cutting actionwhile still in plastic state. The procedures disclosed in Patents Nos.2,856,291 and 2,857,281 are admirably suited for accomplishing thisreduction of the emulsion into particulate form. i

It is evident from the foregoing that when the hot emulsion of flavoringagent, sucrose ester, and sugar base is cooled, a solid emulsion isformed containing the flavoring agent as minute globules uniformlydispersed throughout a continuous phase ofsolid, amorpheussu ar base.The sucrose ester also constitutes part of the solid emul sion but it isnot known whatproportion of the ester is associated with the dispersephase (flavoring agent) or with the continuous phase'isuganba's'e). Itis believed, however, that the sucrose ester is' less concentrated ineitherof these phases than it is at the interface between thephases.

The products of the invention are admirably suited for flavoring foodsof all kinds. For example, they may be incorporated with productsproduced by dehydration of fruit juices to restore flavor lo'st'iri thevarious steps oi dehydration. The resulting flavor fortified dehydratedproducts when reconstituted with water form juices of good, naturalflavor and aroma Any desired volatile flavoring agent may beincorporated with the sucrose ester and sugar base in accordance withthe invention. Illustrative examples are orange oil, lemon oil,grapefruit oil, lime oil, clove oil, peppermint oil, bay oil, cedarwoodoil, apple essence, pear essence, pineapple essence, grape essence,peach essence, apricot essence, strawberry essencejraspberry essence,cherry essence, prune essence, plumessence','cinnamon oil, oil ofnutmeg, oil of sage, oilfof'bitter almonds, cassia oil, teaseed oil,coflee essence, and so forth. Mixtures of flavoring agents may of coursebe employedl In the case 01": fruit essences, such as those enurneratedabove, it is preferred to first purify them to remove water andlowmolecular weight alcohols by the proce'ssdescribed in the patentapplication of K. P. Dirnick'and B. Makower, Serial No. 368,016, filedJuly 14, 1953, now Patent No. 2,904,440. Instead of, or togetherwith,natural flavoring principles, synthetic flavoring agents may beemployed. Illustrative examples are the edible flavor-and aromabearingaldehydes, alcohols, esters, keton'es, phenols, and lactones, forinstance, methyl .anthranilate, decanal, nonanal, Yundiecana'l,cinn'amic aldehyde, geraniol, menthol, methyl salicylat'e, phenylethyl'alcohol; diacetyl, citronellol, citralfand so forth. 'The' proportion offlavoring agent to be incorporated in the sugarbase may be varieddepending on the .flavor strength desired in the final product. Usuallyenough of the flavoring agent is added to furnish about from 5 to 25%thereof in the emulsion.

The sugar baseused in preparing the flavoring compositions of theinvention may hea sugar or a mixture of any two or more sugars. The basemay thus be defined as consisting essentially of saccharides. Varioussugars maybe used as ior cxample sucrose, dextrose, maltose, levulose,lactose, mannose, galactose, invert sugar, corn sugar, .corn syrupsolids, etc. Amixture of sugars if preferably employed to ensure theformation .of an amorphous mass when the hot emulsion is cooled. Anexample of a sugar base is amixture of sucrose with 10 to50.% of adifferent sugar such ,as dextrose, corn syrup, corn syrup solids,maltose, iructose, lactose, or invert sugar. Another example is .asugar-base containing parts sucrose and about .33 parts of invert .sugaror corn syrup solids. For-best results it is preferred to employ as thesugar .base a mixture containing the following ingredients, theproportions of which are given on a dry basis- Proportion, percent Thebase containing these ingredients is preferred as it is especiallyresistant to crystallization. Thus the base will not crystallize in thepreparative stages when the molten base is subjected to shearingstresses as encountered in the pump, mixer, extruder or other devicesused in forming the composition. This is an especially noteworthycharacteristic of the base as ,suchstresses are notorious for theirability to induce crystallinity in various substrates. Moreover, thefinal solid product will retain its amorphous state even when exposed tomoist air or similar influences which tend to promote crystallization.Also the base containing the above ingredients has superiorcharacteristics, as regards melting temperature and viscosity, tofacilitate incorporation of the flavoring agent and sucrose ester, tofacilitate shaping of the hot melt as by extrusion, and to obtain rapidsetting of the hot melt to yield hard, non-sticky, amorphous products.These advantages are further explained as follows: The base liquefies attemperatures which are low enough-so that the flavoring agent andsucrose ester may be incorporated therein without decomposition of anyof the components of the mixture. At the same time the base in theliquefied state exhibits a proper viscosity for shaping it by such meansas extrusion through an orifice. In such event a stream of uniform crosssection can be readily obtained. Moreover, the base exhibits a highcoefficient of viscosity, meansing that the viscosity increases sharplywith decreasing temperature. The advantage of this attribute is thatwhen the hot emulsion is contacted with air or other cooling medium itrapidly increases in viscosity to such an extent as to form a hard,glassy, non-sticky, amorphous mass. The rapidity with which thissolidification occurs facilitates preparation of the final product andavoids any possibility of particles of the final product from stickingto one another. The preparation of flavoring compositions using as thebase the aforementioned mixtures of sucrose, latctose, maltose,dextrose, with or without added dextrin, are disclosed and claimed inthe copending application of T. H. Schultz Ser. No. 719,458, filed March5, 1958.

In preparing the sugar base described immediately above, it is generallypreferred to employ corn syrup (or corn syrup solids) as the source ofsome of the ingredients particularly maltose, dextrose, and dextrin.Depending on the type of corn syrup used these ingredients may besupplied in the proper proportions so that the individual componentsneed not be added as such. Thus for example maltose is preferablysupplied as corn syrup of the high maltose type. This grade of cornsyrup is to be differentiated from the common mediumor high-conversioncorn syrups of commerce which are of the highdextrose type containing alesser proportion of maltose than dextrose. Use of the high-maltosesyrup (or the solids derived therefrom) eliminates for using isolatedmaltose which is quite expensive. Where a corn syrup (or corn syrupsolids) is used to supply some of the ingredients, a small proportion ofhigher sugars will be added via the corn syrup. These higher sugars arenot detrimental and their presence may even be advantageous in the sugarbase.

The invention is further demonstrated by the following illustrativeexamples. For comparative purposes, procedures not in accordance withthe invention are included. Percentages of orange oil are given on avolume/weight basis, abbreviated v./w. A proportion of 8.6% v./w.,

'6 for example, means 8.6 milliliters of orangeoil per grams totalweight'of product.

. 7 Example I The ingredients listed below were mixed together andboiled until the temperature of the mixture increased to 150 0., thus toprepare a molten sugar base.

Ingredient: Parts Sucrose 60 Lactose 20 Dextrose 22 Corn syrup 60 Water23 The corn syrup was a high-maltose type syrup containing 81% solids,these solids being composed of- Percent Dextrose 21.5 Maltose 49.9Higher sugars 6.7 Dextrin 21.9

The composition of-the sugar base is given below on a dry weight basisand accounting for the several ingredients in the corn syrup- Example 11A series of solid flavoring compositions were prepared using the sugarbase prepared as described in Example I. The following procedures Wereused- Run 1 (in accordance with the invention): A portion of the moltensugar base was stirred with sucrose dipalrnitate (0.5% based on dryweight of the sugar base) and the mixture was cooled to 135 C. Then,while constantly stirring, orange oil was added over a period of about 6minutes. The orange oil was added by pumping it into the sugar basethrough a tube dipping into the sugar base and terminating at a pointjust above the stirring impeller to avoid contact with the air. Theamount of orange oil was that required to furnish 8.60% (v./W.) thereofbased on the total weight of the product. After addition of the orangeoil, the emulsion was stirred a minute more; then the emulsion waspoured onto a stainless-steel sheet in a layer about to inch thick. Thismass was allowed to cool and solidify in a room having normaltemperature and low humidity. The solidified material was then ground bypassing it several times through a coffee mill. The ground product wasthen screened, the 10 to.20 mesh particles being retained as finalproduct. This product was then held in a chamber under vacuum (0.02 mm.Hg) for 16 hours to remove the portion of, the orange oil on the surfaceof the particles. This portion of the oil being on the surface is notstabilized or locked-in, hence is best removed as it will deteriorate onstorage of the product.

Run 2 (control): The process as described above in reference to run 1was repeated with the sole exception that the sucrose dipalmitate wasomitted.

Run 3 (not in accordance with the invention): The process as describedabove in reference to run 1 was re peated with the sole exception thathe sucrose dipalmitatewas replaced by a commercial monoglyceride offat-form ing fatty acids. This substance contained 61-66% mono--glycerides, most of the remainder being diglycerides. It was employed inproportion of 1%, based on the dry weight of the sugar base.

- portion of 1%, based on the dry iyei'ght' or the sugar ea e.

The products see ed as above describd"w're their subjected to analysisto determine the actual content of orange oil therein. From theseanalyses and the original theoretical oil content (8.60% v./w.) theloss-of orange oil in each case was calculated. The results obtained aretabulated belowa r n oil content of product; percent Loss 0! orange 01],per- A en a de cent sucrose dipalmita none po yoxyethyleue sort rate.

It is evident frorn the aboye data that in run 1 wherein sucrosedipalmitate was employed, the loss of oil was rela iv y ns n ficant (9%)HQaeYer this resu t i in sharp contrast to the other runs (not inaccordance with the inyeution) wherein considerable losses (31 to 51%) foi ask Pla Ha in thus describe-.5 the invsntiqn What is claime T eapssss which campuse ia q q ns a velai e. l u d fle ariaa asset and a ee-ital est r of su ith her atty acid imp a h t m t n s r base, an oo nthe resultin 1. t 9 a Solid fla composition.

2. The process of claim 1 wherein the said ester of sucroseis sucrosedipahnitate.

3. A solid emulsion. ontaining a vo ati liquid v ing agent and a partialester of sucrose with'a higher fatty acid, in an amorphous sugar base;

4. The product of c1aim3 wherein the said ester of sucrose is sucrosedipalmitate.

Refe en es Cites! s he tilt o this Pa ent uurrao STATES PaTEN-Ts

1. THE PROCESS WHICH COMPRISES INCORPORATING A VOLATILE, LIQUID FLAVORING AGENT AND A PARTIAL ESTER OF SUCROSE WITH A HIGHER FATTY ACID INTO A HOT, MOLTEN SUGAR BASE, AND COOLING THE RESULTING HOT MIX TO FORM A SOLID FLAVORING COMPOSITION. 